CN1261110A - Main component of brightening agent for galvanization and brightening agent prepared from it - Google Patents
Main component of brightening agent for galvanization and brightening agent prepared from it Download PDFInfo
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- CN1261110A CN1261110A CN 99116024 CN99116024A CN1261110A CN 1261110 A CN1261110 A CN 1261110A CN 99116024 CN99116024 CN 99116024 CN 99116024 A CN99116024 A CN 99116024A CN 1261110 A CN1261110 A CN 1261110A
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- brightening agent
- host
- nitrogen
- containing heterocycle
- thiocarbamide
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Abstract
A main component of brightening agent for galvanization is the copolymer of nitrogenuous heterocyclic compound, epihaloalcohol and one or more nitrogenous compounds of amidine and/or carbamide and/or thiourea. The brightening agent contains said main component, polyvinyl imide and/or polyvinyl alcohol and can be used for galvanization for higher brightness of plated layer and quality. Furthermore, said main component is a three-element copolymer only with carbamide and/or thiourea for lower cost.
Description
The brightening agent that the invention belongs to a kind of zinc-plating additive host and form with itself and ancillary component.
Since the sixties; in order to guarantee further to reach requirement on environmental protection on the coating performance good basis; mainly be to adopt low cyanogen, little cyanogen and cyanogenless electroplating technology in zincincation, promote this technology progressive key to be to develop high performance electroplating additive.Since 80 offsprings, for the low chromium of scalable use, the requirement of ultralow chromium passivating technology, and further improve galvanized state of the art, electroplating industry is brought into use special-purpose organic synthesis zinc-plating brightener, to obtain the surfacing of high brightness, domestic no cyanogen zincate galvanizing additive mainly is the reaction product of development amine or various kinds of amine and epoxy chloropropane, little cyanogen and low-cyanide zinc plating additive then mainly develop the reaction product of nitrogen heterocyclic ring and epoxy chloropropane, be aided with certain aldehyde compound again, this class additive all exists luminance brightness low, consumption is big, the narrow deficiency that waits of optimised process scope, then price is higher for the combined electroplating additive of some multiple organic synthesis products of external import, has limited on a large scale and has promoted the use of.
The present invention aims to provide and a kind ofly is applicable to low cyanogen, little cyanogen and does not have the brightening agent host of cyanogen zincate galvanizing technology and the brightening agent of forming with itself and other ancillary component, the brightening agent available of forming with this brightening agent host and other ancillary component can be good, the zinc coating of full specular light brightness.
Further purpose of the present invention provides a kind of zinc-plating brightener host that can further reduce cost on the basis that achieves the above object.
The technical scheme that realizes above-mentioned purpose is: brightening agent host of the present invention is nitrogen-containing heterocycle compound and epihalohydrin and another nitrogenous compound amidine, and/or guanidine, and/or urea, and/or the reactant of a kind of or several terpolymers generations in the thiocarbamide;
Its preparation process is in two steps:
1-1, fully react with at least a nitrogen-containing heterocycle compound and one or more epihalohydrins and to obtain intermediate;
Reaction medium is generally water, the mol ratio of its reaction (being the mole ratio of nitrogen-containing heterocycle compound and epihalohydrin)
Be 1: 0.2～5;
Its preferred version is 1: 1.1～1.3;
1-2, a kind of or several reactions in above-mentioned intermediate and nitrogenous compound amidine, guanidine, urea, the thiocarbamide are obtained this light
Bright dose of host; The mol ratio of this reaction in step (be nitrogen-containing heterocycle compound and nitrogenous compound amidine, guanidine, urea,
The mole ratio of thiocarbamide) be 1: 0.05～5;
Its preferred version is 1: 0.08～0.3;
Detailed process is: earlier with a kind of in amidine or urea or thiocarbamide or the guanidine or several are soluble in water, and pH value is transferred to
The alkaline range of 8-14 adds the intermediate that the first step reaction makes again, and temperature of reaction is 70～98 ℃, is returning
Constant temperature is 3～4 hours under the stream temperature, promptly gets this brightening agent host.
Nitrogen-containing heterocycle compound recited above can be the nitrogen-containing heterocycle compound that contains one, two, three nitrogen-atoms, as pyridine, pyrroles, imidazoles, pyrazoles, 1,2, and 3 azoles, piperazine, the saturated cyclic amines or derivatives thereof, its typical structure general formula is:
N in the formula
1+ n
2=5 or 6
Its derivative is meant that the hydrogen atom of imido grpup or ring hydrogen atom are replaced and the derivative such as the 1-Methylimidazole of generation glyoxal ethyline, 1 by hydroxyl, alkyl, amino or ethanoyl; the 4-methylimidazole, 4-hydroxyl-2 aminooimidazole, 2; the 5-dimethyl, 1-N-ethyl pyrrole N-, 2-methylpyrazole; the 4-methylpyrrole, N methyl piperazine, N; the N-lupetazin; 2,5-lupetazin, ethyleneimine; tetramethyleneimine; the N-crassitude, piperidines, 1-methyl piperidine; 2; the 6-lupetidine, 3,5-lupetidine etc.
Described nitrogenous compound amidine, guanidine, urea, the general structure of thiocarbamide is
R wherein
1, R
2Be hydrogen or lower alkyl, aryl or cyano group, M is N, O or S, also can select the salt such as the guanidine of base acid for use, Guanidinium hydrochloride, guanidine sulfate, carbonamidine, hydrochloric acid carbonamidine, acetic acid ethanamidine, hydrochloric acid benzene carbon amidine, cyano amidine, thiocarbamide, vinyl thiocarbamide, urea element, iminourea etc.
The further preferred version of brightening agent host of the present invention is that it is the reactant of nitrogen-containing heterocycle compound and epihalohydrin and urea and/or thiocarbamide terpolymer generation.
The brightening agent that brightening agent host of the present invention and ancillary component are formed comprises the component of following proportioning:
Brightening agent host: polymine and/or polyvinyl alcohol
＝0.01～10g/l∶0.01～5g/l
Wherein: polymine polymerization degree preferable range is 1000～1500;
Polyvinyl alcohol polymerization degree preferable range is 1500～1700;
The another kind of brightening agent that brightening agent host of the present invention and ancillary component are formed comprises the component of following proportioning:
Brightening agent host: 1-phenmethyl pyridine carboxylic acid salt
＝0.01～10g/l∶0.05～20g/l
The zinc-plating brightener of forming with brightening agent host of the present invention and other ancillary component is used for cyanogen, low cyanogen, little cyanogen and does not have the zincate basic plating zinc solution of cyanogen, can obtain smooth in the inherent negative electrode of the processing condition scope of broadness, fine and close, bright, the no brittle galvanic deposit zinc coating of minute surface, dispersive ability and covering power are good, the current efficiency height, steady quality.
The further scheme of the present invention adopts the terpolymer of urea and/or thiocarbamide to make brightening agent host then can significantly reduce brightening agent under the prerequisite that guarantees the above-mentioned quality of coating of the present invention cost, for large-scale application has been created condition.
Brightening agent host embodiment 1:
The first step is that 68 parts of imidazoles are dissolved in 200 parts of water, is preheating to 35 ℃, and 110 parts of points of epoxy chloropropane are added dropwise to, cause is thermopositive reaction, need the cooling of cooling jacket or cooling tube,, make intermediate to keep temperature of reaction at 75～80 ℃, second step was with 9.5 parts of 60 parts of water dissolution guanidine sulfates, with 50% aqueous sodium hydroxide solution pH value is transferred to 10, this solution is added the first step react in the intermediate that makes, reaction is 3 hours under reflux temperature, product is reclaimed in cooling.
Brightening agent host embodiment 2:
The first step is that 50 parts of piperazines are dissolved in 200 parts of water, be preheating to 25 ℃, 100 parts of points of epoxy chloropropane are added dropwise to, lower the temperature with cooling tube, to keep temperature of reaction at 80～90 ℃, make intermediate, second step was with 8 parts of 50 parts of water dissolution thiocarbamides, with 50% aqueous sodium hydroxide solution pH value was transferred to 10, this solution is added the first step to react in the intermediate that makes, reaction is 3 hours under reflux temperature, and product is reclaimed in cooling.
Brightening agent host embodiment 3～8 component tables: embodiment composition weight mol numerical example 3 imidazoles 27.2g 0.4
Water 100ml
Epoxy chloropropane 48.8g 0.53
Guanidine sulfate 8g/35ml water 0.038 example 4 imidazoles 27.2g 0.4
Water 100ml
Epoxy chloropropane 48.8g 0.53
Dicyanodiamide 5g/20ml water 0.06 example 5 imidazoles 27.2g 0.4
Water 100ml
Epoxy chloropropane 48.8g 0.53
Guanidinium hydrochloride 3.8g/20ml water 0.04 example 6 glyoxal ethyline 37g 0.45
Water 100ml
Epoxy chloropropane 50g 0.55
Hydrochloric acid carbonamidine 3.8g/20ml water 0.04 example 7 imidazoles 13.6g 0.20
Glyoxal ethyline 18.8g 0.23
Water 100ml
Epoxy chloropropane 48.8g 0.53
Thiocarbamide 4.6g 0.06 example 8 1,2 dimethylimidazole 45g 0.45
Water 100ml
1,2, dichlorohydrine 70.9g 0.55
Plain 3g 0.05 example of urea 9 imidazoles 20g 0.3
1,2 dimethylimidazole 25g 0.25
Water 100ml
Epoxy chloropropane 50g 0.55
The plain 1.8g 0.03 of urea
Thiocarbamide 1.5g 0.02 example 10 imidazoles 13.6g 0.20
1,2 dimethylimidazole 24.6g 0.3
Water 100ml
Epoxy chloropropane 50g 0.55
The plain 1.5g 0.02 of urea
Guanidinium hydrochloride 4.3g/20ml water 0.02 brightening agent host of the present invention cooperates the brightening agent of forming with other ancillary component: embodiment 2-1:
Brightening agent host: 0.1～3g/l
Polymine (polymerization degree 1500): this example of 0.2～3g/l light district is broad, and coating is evenly smooth, low district light and smooth raising.Embodiment 2-2:
Brightening agent host: 0.5～5g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.5-10g/l
This routine Zhong Gao district reaches the minute surface light, and bright dipping is quick, and current efficiency is also higher.Embodiment 2-3:
Brightening agent host: 6～8g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.8-10g/l
This routine low current density district luminance brightness of polymine (polymerization degree 1500): 0.1～3g/l is particularly outstanding, is suitable for barrel plating production.Embodiment 2-4:
Brightening agent host: 3～5g/l
1-phenmethyl pyridine-4-carboxylic acid sodium: 0.5～10g/l
Polymine (polymerization degree 1000): this routine effect of 0.5～5g/l is near embodiment 2-3.Embodiment 2-5:
Brightening agent host: 0.5～5g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.8～8g/l
Polyvinyl alcohol (polymerization degree 1700): this example of 0.05～2g/l allows high current density, and deposition speed is very fast.Embodiment 2-6:
Brightening agent host: 0.2～0.8g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.5～5g/l
Polymine (polymerization degree 1500): 0.01～1g/l
Hexamethylenetetramine and epoxy chloropropane synthetics: 0.1～5g/l
This example coating in wide current density range is smooth, bright.
Embodiment 2-7:
Brightening agent host: 0.5～10g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.5～20g/l
Polyvinyl alcohol (polymerization degree 1500): 0.1～5g/l
Trolamine, quadrol and epoxy chloropropane synthetics: 0.5～10g/l
This routine coating minute surface luminosity is outstanding.
Embodiment 2-8:
Brightening agent host: 0.01～2g/l
1-phenmethyl pyridine-3-carboxylic acid sodium: 0.05～5g/l
Diethanolamine, dimethylaminopropylamine and epoxy chloropropane synthetics: 0.5～20g/l.
This example is particularly useful for little cyanogen or cyanide-free plating bath.
The brightening agent that brightening agent host of the present invention and ancillary component are fitted in is applicable to middle cyanogen, low cyanogen, little cyanogen and does not have the zincate basic plating zinc solution of cyanogen, exemplifies the formula range of its exemplary application in alkaline zinc plating liquid below:
The low little cyanogen of cyanogen of middle cyanogen does not have cyanogen zinc oxide ZnO (g/l) 15～25 10～15 9～12 8～15 sodium cyanide NaCN (g/l) 25～40 15-20 4～6 0 sodium hydroxide NaOH (g/l), 70～80 70～80 70～80 80～120 yellow soda ash Na
2CO
3(g/l) 15～20 15～20 15～20 10～20 brightening agents of the present invention (g/l) 0.01～15
Adopt above-mentioned technical recipe, at 15～45 ℃ of temperature, 0.5～10A/dm
2The coating that cathode of electrolytic tank obtains under the wide current density district processing condition is smooth, fine and close, bright, the no fragility of minute surface.
Lift an application example that adopts brightening agent that this brightening agent host and ancillary component fit in and alkaline zinc plating liquid to be used below:
Zinc oxide ZnO 12g/l
Sodium hydroxide NaOH 80g/l sodium cyanide NaCN 15g/l yellow soda ash Na
2CO
320g/l brightening agent host (effective constituent) 1g/l brightening agent ancillary component 1-phenmethyl pyridine carboxylic acid salt 0.8g/l
Polyvinyl alcohol (PVA) 0.05g/l current density 0.5～10A/dm
2The pure zinc (1 of 20～50 ℃ of cathode materials of temperature
#) anode and cathode area be than 1.2～1.5: 1 can obtain the no brittle electrodepositing zinc coating of minute surface light in the current density district of above-mentioned such broadness.
Claims (7)
1, a kind of zinc-plating brightener host, this host are nitrogen-containing heterocycle compound and epihalohydrin and another nitrogenous compound amidine, and/or guanidine, and/or urea, and/or the reactant of a kind of or several terpolymers generations in the thiocarbamide;
Its preparation process is in two steps:
1-1, fully react with at least a nitrogen-containing heterocycle compound and one or more epihalohydrins and to obtain intermediate;
Reaction medium is generally water, the mol ratio of its reaction (being the mole ratio of nitrogen-containing heterocycle compound and epihalohydrin)
Be 1: 0.2～5;
1-2, a kind of or several reactions in above-mentioned intermediate and nitrogenous compound amidine, guanidine, urea, the thiocarbamide are obtained this light
Bright dose of host; The mol ratio of this step reaction is 1: 0.05～5;
Nitrogen-containing heterocycle compound recited above can be the nitrogen-containing heterocycle compound or derivatives thereof that contains one, two, three nitrogen-atoms, and its typical structure formula is:
N in the formula
1+ n
2=5 or 6
Its derivative is meant that the hydrogen atom of imido grpup or ring hydrogen atom are replaced and the derivative of generation by hydroxyl, alkyl, amino or ethanoyl.
Described nitrogenous compound amidine, guanidine, urea, the general structure of thiocarbamide is
R wherein
1, R
2Be hydrogen or lower alkyl, aryl or cyano group, M is O, N or S, also can select the salt of base acid for use.
2, zinc-plating brightener host according to claim 1 is characterized in that it is the reactant of nitrogen-containing heterocycle compound and epihalohydrin and urea and/or thiocarbamide terpolymer generation.
3, zinc-plating brightener host according to claim 1 and 2 is characterized in that: the mol ratio of its reaction is 1: 1.1～1.3 in described 1-1 the first step preparation process, and the mol ratio of reacting in described 1-2 second step preparation process is 1: 0.08～0.3.
4, the brightening agent of being made up of the described brightening agent host of claim 1 to 3 comprises the component of following proportioning:
Brightening agent host: polymine and/or polyvinyl alcohol
＝0.01～10g/l∶0.01～5g/l
5, brightening agent according to claim 4 comprises the component of following proportioning:
Brightening agent host: polymine and/or polyvinyl alcohol: 1-phenmethyl pyridine carboxylic acid salt
＝0.01～10g/l∶0.01～5g/l∶0.05～20g/l
6, the brightening agent of being made up of the described brightening agent host of claim 1 to 3 comprises the component of following proportioning:
Brightening agent host: 1-phenmethyl pyridine carboxylic acid salt
＝0.01～10g/l∶0.05～20g/l
7, brightening agent according to claim 6 comprises the component of following proportioning:
Brightening agent host: 1-phenmethyl pyridine carboxylic acid salt: amine and epihalohydrin reactant
＝0.01～10g/l∶0.05～20g/l∶0.1～10g/l
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116024A CN1117177C (en) | 1999-01-21 | 1999-01-21 | Main component of brightening agent for galvanization and brightening agent prepared from it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116024A CN1117177C (en) | 1999-01-21 | 1999-01-21 | Main component of brightening agent for galvanization and brightening agent prepared from it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1261110A true CN1261110A (en) | 2000-07-26 |
| CN1117177C CN1117177C (en) | 2003-08-06 |
Family
ID=5278876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99116024A Expired - Fee Related CN1117177C (en) | 1999-01-21 | 1999-01-21 | Main component of brightening agent for galvanization and brightening agent prepared from it |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1932084B (en) * | 2006-08-25 | 2010-05-12 | 卢月红 | Noncyanide electroplating solution additive and preparation process of noncyanide electroplating solution |
| CN101565839B (en) * | 2009-04-28 | 2011-04-06 | 武汉风帆电镀技术有限公司 | Cyanogen to cyanogen-free alkali environment-friendly galvanizing brightener |
| CN102304731A (en) * | 2011-08-23 | 2012-01-04 | 武汉吉和昌化工科技有限公司 | Wide temperature, wide current and wide brightness type cyanide-free alkaline zinc plating process |
| CN103014785A (en) * | 2013-01-08 | 2013-04-03 | 广州博泉环保材料科技有限公司 | Electroplating solution, preparation method thereof and galvanization technique utilizing electroplating solution |
| CN105336993A (en) * | 2014-06-30 | 2016-02-17 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN106086969A (en) * | 2016-08-29 | 2016-11-09 | 宁波江东甬风工业设计有限公司 | A kind of preparation method of strong associativity zinc-plating brightener |
| CN106319587A (en) * | 2015-06-30 | 2017-01-11 | 罗门哈斯电子材料有限责任公司 | Surface treatment solutions for gold and gold alloys |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101555609B (en) * | 2009-04-28 | 2010-08-04 | 武汉风帆电镀技术有限公司 | An environment-protective alkali galvanization composition brightener for transformation from cyanide to non-cyanide |
| JP5731802B2 (en) * | 2010-11-25 | 2015-06-10 | ローム・アンド・ハース電子材料株式会社 | Gold plating solution |
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| JPS5332771B2 (en) * | 1973-12-10 | 1978-09-09 | ||
| US4036206A (en) * | 1976-07-30 | 1977-07-19 | E. I. Du Pont De Nemours And Company | Selective solar energy absorption |
| US4169871A (en) * | 1978-10-12 | 1979-10-02 | Acf Industries, Inc. | Staged carburetor |
| JPS58199889A (en) * | 1982-05-17 | 1983-11-21 | Nippon Kagaku Sangyo Kk | Electrogalvanizing bath |
| US4536261A (en) * | 1984-08-07 | 1985-08-20 | Francine Popescu | Alkaline bath for the electrodeposition of bright zinc |
| CN1013773B (en) * | 1988-04-25 | 1991-09-04 | 东北工学院 | Compound brightener for the use in electrozincing |
| JPH05112889A (en) * | 1991-08-19 | 1993-05-07 | Yuken Kogyo Kk | Zincate-type zinc-iron alloy plating bath |
| CN1039546C (en) * | 1994-01-24 | 1998-08-19 | 厦门大学 | Basic plating method for bright Zn-Ni alloy |
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- 1999-01-21 CN CN99116024A patent/CN1117177C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1932084B (en) * | 2006-08-25 | 2010-05-12 | 卢月红 | Noncyanide electroplating solution additive and preparation process of noncyanide electroplating solution |
| CN101565839B (en) * | 2009-04-28 | 2011-04-06 | 武汉风帆电镀技术有限公司 | Cyanogen to cyanogen-free alkali environment-friendly galvanizing brightener |
| CN102304731A (en) * | 2011-08-23 | 2012-01-04 | 武汉吉和昌化工科技有限公司 | Wide temperature, wide current and wide brightness type cyanide-free alkaline zinc plating process |
| CN103014785A (en) * | 2013-01-08 | 2013-04-03 | 广州博泉环保材料科技有限公司 | Electroplating solution, preparation method thereof and galvanization technique utilizing electroplating solution |
| CN103014785B (en) * | 2013-01-08 | 2014-12-24 | 广州博泉环保材料科技有限公司 | Electroplating solution, preparation method thereof and galvanization technique utilizing electroplating solution |
| CN105336993A (en) * | 2014-06-30 | 2016-02-17 | 苏州宝时得电动工具有限公司 | Electrolyte solution and battery |
| CN106319587A (en) * | 2015-06-30 | 2017-01-11 | 罗门哈斯电子材料有限责任公司 | Surface treatment solutions for gold and gold alloys |
| CN106319587B (en) * | 2015-06-30 | 2018-06-22 | 罗门哈斯电子材料有限责任公司 | For gold and the surface processing solution of billon |
| CN106086969A (en) * | 2016-08-29 | 2016-11-09 | 宁波江东甬风工业设计有限公司 | A kind of preparation method of strong associativity zinc-plating brightener |
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